Bleach fast reactive dyes



United States Patent 1. 3,040,022 BLEACH FAST REAC'IlVE DYES Roy E.Starn, Wilmington, Del., assignor to E. I. du

Pont de Nemours and Company, Wilmington, Del., a

corporation of Delaware No Drawing. Filed Nov. 7, 1958, Ser. No. 772,425

3 Claims. (Q1. 260153) to yellow, and being characterized particularlyby fastmess to bleach. Other objects and achievements of this inventionwill become apparent as the description proceeds.

Reactive dyes constitute a new type of dyes of relatively recentdevelopment. In these dyes, the dyeing capacity depends, not on aflinitybetween the dye and fiber, but on direct chemical reaction (withcovalent bonds) between the dye and certain reactive radicals in thefiber. The dyes in such cases may possess chloro-triazine radicals,which react with 01-1 and NH radicals occurring in the fibers. Hitherto,however, dyes of the reactive type have been deficient in bleachfastness, e.g., to treatment with sodium hypochlorite such as oftenfollows or accompanies launden'ng, at home or in commercialestablishments. Some of the reactive dyes now on the market are somewhatimproved in this respect, and will withstand, for instance, treatmentwith chlorine at a concentration of 0.01% by weight of the treatmentbath, but are nevertheless fugitive to bleach at a concentration of 0.3%by weight. Since commercial laundering often uses bleach baths of thehigher concentration, it is clear that the bleach fastness of such acommercial dye is far from satisfactory.

I have now found that bright fiber-reactive dyeings, from an aqueous dyebath, in shades ranging from greenish-yellow to yellow, andcharacterized by outstanding fastness to bleach (even at chlorineconcentrations of 0.3 may be obtained by using the novel azo compoundsof this invention, defined by the formula In this formula, R is abenzenoid radical which may be substituted by C1, CH C H OCH or $0 M; Ris a benzenoid radical which may be substituted by C1, CH C H OCH orCOOH; Z is a radical of the group consisting of CH and C H X is ahalogen atom of the group consisting of Cl and Br; Y is a member of thegroup consisting of Cl, Br, O-alkyl, S-alkyl, NH NH- alkyl, N(alkyl)monoand di-hydroxy-alkylamino, NH- aryl, N-aJk-yl-aryl, wherein ,saidaryls may contain water solubilizing groups selected from sulfo andcar-boxy; the alkyls aforementioned being radicals of lto 4 C-atoms eachand the aryls being aromatic radicals of not more than 10 C-atoms intheir cyclic structure; M is an alkali metal; n is an integer from 1 to4 and designates the number of $0 M radicals in the molecule inclusiveof any that may be present in Y, and at least one of the $0 M radicalsis located in the naphthalene nucleus.

It will be noted that the novel dyes of this invention possess thefollowing characteristics in their structure: They are monoazo dyes,having a triazine radical which bears at leaset one halogen atom (C1 orBr); they possess a 1,2-naphthotriazole radical; the triazine ring isattached to one of the components of the azo dye by means of a secondaryamine radical; the entire molecule contains at least 2 and up to 6 or 7sulfo groups, of which at least one is located in the naphthalenenucleus, and the dye chromophore, that is, the dye molecule exclusive ofthe triazine ring and its substituents, is free of OH and NH groups.

In addition to possessing outstanding fastness to bleach, the dyeingsproduced by my novel dyes possess other desirable qualities, such asgood fastness to light and good fastness to after-treatment withtextile-finishing resins (such as crease-proofing or fiber-settingresins).

Generally speaking, my novel compounds. are synthesized by diazotizing anitroarylamine, such as por mnitroaniline, and coupling same to an alphaor beta naphthylamine sulfonic acid (1 to 3 SO H groups); oxidizing theortho amino azo compound thus obtained in conventional manner (cupricsulfate or sodium hypochlorite) to produce a nitroarylnaphtho triazolecompound; reducing the nitro group to the amine stage; diazotizing andcoupling to a secondary aryl amine of the formula R -NHZ, wherein R andZ are as above defined, and -then condensing the aminoazo dye thusobt-ained with a dihalogenoor trihalogeno-triazine com pound of theformula wherein X and Y are defined as above.

When Y is halogen, the said condensation is effected at ice temperatures(0 to 5 C.) in aqueous medium, whereby the resulting end productpossesses two halogen atoms on the triazine ring. But if the reactivedye is to contain only one halogen in the triazine ring, either one oftwo routes may be resorted to: (a) reaction of the aminoazo compound,mole per mole, with a cyanuric halide, followed by reaction with onemole of a compound which introduces a Y group other than halogen, or (b)first reacting a compound of the latter group, mole per mole, with acyanuric halide, followed by reaction with one mole of the aminoazo dye.In either route, the reaction with cyanuric halide is eifected at icetemperatures (0 to 5 C.) in aqueous medium, and the second halogen atomon the triazine ring is reacted at a temperature in the range of 10 to70 C., likewise in aqueous medium.

The compounds which are employed to form a Y group other than halogenare, for instance, a lower alcohol (1 to 4 C-atoms), a lower mercaptan,a monoalkylamine, a dialkylamine, an alkanolamine, an arylamine, an N-alkyl-arylamine, or an arylor N-alkylarylamine bearing from 1 to 3water-solubilizing groups (e.g. SO H or COOH).

The final dye is generally salted out with common salt; hence its sulfogroups have the form SO Na. It may, however, be also recovered, in knownmanner, in the form of a potassium or lithium salt, or it may beconverted into one or the other of these salts, in known manner, afterisolation in the form of sodium salt.

Without limiting this invention, the following examples acid. Theaminoazotriazole compound (II) added an acetone solution containing 57parts of cyanuric 3,040,022 3 I 4 Example 1 pH to 6.5. After stirringfor 30 minutes, the reaction to A quantity of p-nitroaniline wasdiazotized in conven- I dichlorotriazine (III) (III) was complete. Thissolution of (III) was divided into three equal portions.

To one-third of the above solution at 15 C. there were added 11.3 partsof aniline. The solution was maintained at pH 7 to 8 for onehour by thedropwise addition of a sodium hydroxide solution. The dye solutiontional manner and coupled to 8-amino-1,3,6-naphthalenetri(sodiumsulfonate).- Upon salting out and filtering of the product, it wassubjected to oxidation in conventional manner (using cupric sulfate andammonia; see, for instance Example 1 of U.S.P. 2,700,044) to form thep-nitrophenyl-l,Z-naphthotriazo-le. The product was was heated to andSumcient .NaCl was added to again isolated and subjected to reductionwith iron and produce a c Solution by Volume The product acetic a P t0to reduce The ni'tfo group was separated by filtration and dried. Theisolated prodto the amino stage. The aminotriazole thus produced notwhich is believed to have the structure corresponds to the formula is ayellow-brown powder which dissolves in water to N80 8 give a yellowsolution. When applied to cotton broad- 3 cloth from an aqueous bath bythe method described in L Example 11 hereinbelow, it exhibits a brightyellow shade having excellent light and wash ifastness and outstandingNaozs scam (I) fastness to chlorine bleach and to peroxide.

To a solution of 170 parts of the aminotriazole (I) Examp 1e 2 and 21.4parts of sodium nitrite in 710 parts of water at If in Example 1,one-third of the solution of dichloropH 9 and at 10 C., were added 103parts of 10 N hy- 40 triazine (III) is treated with 12.6 parts ofdiethanolamine drochloric acid. After stirring for one hour at 10 toinstead of 11.3 parts of aniline, there is obtained another 15 C. theexcess nitrous acid was removed with sulfamic yellow dye of the probablestructure CH; N N

NaO S- -SO;Na 01 When applied to cotton broadcloth from'an aqueous bathby the method described in Example 11 hereinbelow, it

Nao s N NO ;C has similar shade and fastness properties to the dye of II! l I Example 1. r

Example 3 If in Example 1, one-third of the solution of dichloro- (H)triazine ('III) is treated with 10.7 parts of 3-methoxypropylamineinstead of 11.3 parts of aniline, there is obwas prepared by adding 34.5parts of N-methylaniline tained athird yellow dye of probable structureNa0 S I]I-N N: r r-uncmomcmocns I CH: N N v "N 5 SOrNa o1 Nil-03S andstirring overnight. The coupling solution was cooled When applied tocotton broadcloth from an aqueous bath to 0 to 5 C. by the addition ofice. There was then by the method described in Example 11 hereinbelow,it has similar shade and 'fastness properties to the dye of Example 1.

chloride. Simultaneously there-were added 67 parts of v In a similarmanner, the dichlorotriazine (III) may be '5 N NaOH so as to maintain apH of 2. Then another 7 160 parts of 5 N NaOH were added, so as to bringthe reacted with a lower alcohol, e.g. methyl, ethyl or butyl dissolving10.3 parts of sodium metanilate in 40 parts of Example 4 The product wasagain isolated and subjected to reduction with iron and acetic acid incustomary manner to reduce the nitro group to an amino group. Theaminotriazole thus produced corresponds to the formula 5 If, in Example1, the solution of dichlorotriazine (III) com is salted and theprecipitate is separated by filtration and dried, the resultant yellowpowder corresponds to Formula lap-N (111). When applied to cottonbroadcloth from an aqueous bath by the method described in Example 12hereinbelow. it exhibits a slightly greener shade than the dye ofExample 1. It has excellent light and wash fastness and outstandingfastness to chlorine bleach and to peroxide. 7

sosNa NaO S SOaNa This aminotriazole was diazotized and coupled toN-methylaniline, condensed with cyanuric chloride to form adichlorotriazine and this dichlorotriazine was then condensed withaniline according to the methods described in Example 1. The structureof the product is believed to be Example 5 15 A slurry was prepared bydissolving 9.78 parts of cyanuric chloride in 51 parts of acetone andadding this solution to a mixture of 83 parts of water and 93 parts Whendyed by the procedure described in Example 11 hereinbelow, it gives aredder-yellow shade than that obtained from the dye of Example 1. Thedye of this example also has excellent light and wash fastness andoutstanding fastness to chlorine bleach.

of ice. To the slurry was added a solution prepared by water and 34parts of ice, adjusting the pH to 5 and adding 7.62 parts of crystallinesodium acetate. After there was no longer diazotizable amine present,the pH was adjusted to 5.5 with 6.6 parts of 10 N NaOH and 35 then 50parts of water were added. This solution of primary condensation productof sodium metanilate and cyanuric chloride was added to a solution ofthe amino- 11.3 parts of the aminotriazole (I) of Example 1 andazotriazole compound (II), of Example 1, which con- 1.52 parts of sodiumnitrite was added 5.8 parts of 10 N tained 30.7 parts of (II) in 310parts of water at pH 5.5 hydrochloric acid. After one hour the excessnitrous acid and at 57 C. The solution was stirred for three hours wasdestroyed with su-Ifamic acid and there was then at to C. while the pHwas maintained at 4.8 to added 2.42 parts of .N-methyl-m-toluidinedissolved in 5.5 by the dropwise addition of 7.2 parts of 10 N NaOH. 25parts of water and 2.3 parts of 10 N hydrochloric acid. The product wasprecipitated by the addition of 155 parts The coupling was stirredovernight at room temperature. of sodium chloride, and separated byfiltration. 45 The solution was adjusted to pH 6 and heated to 55 C.

The isolated product, which is believed to have the To this solution ofarninoazotriazole was added a solu- Erample 8 To a solution at 5 C.consisting of 130 parts of water,

structure, tion of the primary condensation product of cyanuric NaOsS l|lI-N N==N- -Ol l CH: N N

i N50; some NEE-O dorm is a tan power which gives shades on cotton verysimilar chloride and sodium metanilate prepared as follows: A

'to those obtained from the dye of Example 1. solution of 3.9 parts ofsodium metanilate in 22 parts of water was adjusted to pH 6 and 3 partsof crystalline sodium acetate were added. This solution was added to Ifin Example 5 the 10.3 parts of sodium metanilate a slurry prepared byadding a solution of 3.7 parts of are replaced by 13.3 parts of2-amino-p-benzenedisulfonic cyanuric chloride dissolved in 16 parts ofacetone to 30 acid a dye is obtained which is similar in shade andfastparts of ice and 10 parts of water; After there 'was no nessproperties to the dye of Example 5. longer diazotizable amine presentthe pH was adjusted to 6.5 with a sodium hydroxide solution.

. v v The solution of aminoazotriazole and the primary con- A quantityof 3-amino-4-methoxy-6-nitrobenzenesuldensation product at 50 to 55 C,was maintained at pH tonic acid was diazotized in conventional mannerand 5' to 6 by the dropwise'addition of 17.7 parts of 2 N coupled to3-amino-2,7-naphthalene disodium sulfonate, sodium hydroxide. Theproduct was precipitated by the Upon filtering off the product, it wassubjected to oxidaaddition of 70 parts of sodium chloride andseparatedby tion in conventional manner (using sodiumhypochlorite filtration.

in a slightly alkaline solution; see, for instance, Example The isolatedproduct which is believed to have the IV of U .S.P; 2,713,055) to form a1,2-naphthotriazole. structure below is a tan powder which gives dyeingson Example 6 Example 7 cotton very similar to those obtained from thedye of Example 5. V

NaOaS SO;Na

In a similar manner, the N-methyl-m-toluidine used in this example maybe replaced by an equivalent amount of N-ethyl-m-toluidine. m-ethyl(chloro or methoxy)-N- methylaniline or 2,5-dimethyl-N-methylaniline toproduce light fast and bleach fast reactive dyes.

, Example 9 If in Example 8 the N-methyl-m-toluidine is replaced by 3.3parts of N-ethylanthranilic acid the product obtained gives dyeings oncotton which have outstanding fasmess to chlorine bleach.

Example 10 If in Example 8 the aminotriazole (I) of Example 1 isreplaced by 11.3 parts of an aminotriazole of the structure NaOaS NaO SSO;Na

(prepared by using m-nitroaniline instead of p-nitroaniline in theprocess of Example 1) the product obtained gives yellow dyeings oncotton which are somewhat greener in shade than those obtained from thedye of Example 8, and which have outstanding fastness to chlorinebleach.

'The mode of application of my novel compounds to fiber having reactiveOH or NH groups is not much different from that employed with otherreactive dyes now on the market. The following examples will illustratethe procedure:

, Example 11 Dyeing pr0cedz4re.A 4.15% aqueous solution of the dye ofExample 1 was padded on cotton broadcloth at 70 C. in such a manner thatthe increase in Weight by the fabric was 60%. After the fabric was driedit was repadded in the same manner with a solution which contained 25%sodium chloride and 1.2% sodium hydroxide. The wet fabric was steamed ortwo minutes and then scoured at the boil or two minutes with a solutioncontaining 0.3% sodium carbonate and 0.2% of the condensation product ofmoles of ethylene oxide with one mole of a C alcohol. The qualities ofthe dyeing thus produced were as reported in Example 1.

i Example 12 Dyeing procedure.-The dichlorotriazine dye of Example 4 wasapplied to cotton broadcloth in exactly the same manner as described inExample 11 except that the dye solution was padded at room, temperature(20 to C.). The results were as reported in Example 4.

It will be understood that the details of the above examples may bevaried widely without departing from the spirit of this invention. Forinstance, in lieuof the particular ainino-naphthalene-sulfonic acidsnamed in the above examples, any of the following may be used:

6-(or 7-)amino-1,3-naphthalene-disulfonic acid3-amino-l,S-naphthaIene-disulfOnic acidS-amino-1,6-naphthalene-disulfonic acid The in or p-nitroanil-ines named:in Examples 1, 7 and 10 above may be replaced by other morp-nitroanilines C-Cl S O;Na which contain Cl, CH or OCH substituents inany of their remaining positions in the nucleus.

In lieu of the secondary arylamines employed as coupling componentfollowing the second diazotization in any of the above examples, any ofthe following-may be used:

N-methyl-oetoluidine, 5-chloro-2-methyl-N-methylaniline,N-methyl-o-anisidine,

2,5 -dimethoxy-N-methylaniline, 5-methyl-2-methoxy-N-methylaniline,

as well as any of those named in Examples 8 and 9.

In Examples 5, 6, 8, 9 and 10, instead of using the primary condensationproduct of cyanuric chloride and sodium metanilate, other primarycondensation products of cyanuric chloride may be employed. Forinstance, one may use the condensation products of cyanuric chloride (onthe first Cl-atom) with any of the following: ammonia; primary aliphaticamines, such as methylamine, ethylamine, butylamine, monoethanolamine,and 3-methoxypropylarnine; common primary aromatic amines, such as omorp-toluidine, omor p-chloraniline, and anthranilic acid; sulfonatedaromatic amines, such as maminobenzene-sulfonic acid,2amino-rhenzene-disulfonic acid, 7-amino-1,3-naphtha1ene-disulfonicacid, and 8- amino- 1,3,6 naphthalene-trisulfonic acid; secondaryaliphatic amines, such as dimethylamine, dibutylamine,methyliso-propyl-amine, diethanolamine, and N-met-hyl-3-methoxypropylamine; secondary aromatic amines, such as N-methy-lanilineor N-ethyl-mtoluidine; etc.

Other variations in procedure or in choice of initial materials will bereadily apparent to those skilled in the art.

I claim as my invention:

1. A compound of the formula wherein R is a phenylene radical of whoseremaining nuclear valencies at least two are satisfied by hydrogen Whilethe remaining valencies are satisfied by members of the group consistingof H, Cl, CH C H OCH and $0 M, M being an alkali metal; R is a phenyleneradical of whose remaining nuclear'valencies at least two are satisfiedby hydrogen while the remaining valencies are satisfied by members ofthe group consisting of H, Cl, CH C H OCH and COOH; Z is a radical ofthe group consisting of methyl and ethyl; X is a halogen atom of thegroup consisting of Cl and Br; Y is a member of the group consist-ing ofC Br, O-alkyl, S-alkyl, primary amino, monoalkyl amino, diaikylamino,monoalkanol- 9 10 integer from 1 to 4, at least one of the $0 M radicalsbut 2. The compound of the formula Nams Til-N N=NON-(IJ/ -01 I (511s N Nf NaO S some NH-O B 0 Na not more than three being located in thenaphthalene nucleus. 3. The compound of the formula l (I'JHI N N N iN80| SO Na C1 References Cited in the file of this patent UNITED STATESPATENTS 1,667,312 Fritzsche et a1 Apr. 24, 1928 2,493,975 Kaiser Jan.10, 1950 2,795,577 Feeman June 11, 1957 2,860,129 Gunst Nov. 11, 19582,873,269 Fasoiati et a1 Feb. 10, 1959 2,951,071 Tilley Aug. 30, 1960OTHER REFERENCES Gilman: Organic Chemistry, vol. III, pages 293-294.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,040,022 June 19, 1962 Roy E. Starn It is hereby certified that errorappears in the above numbered patmt requiring correction and that theea'id Letters Patent should read as :orrected below.

Column 2, line 57, for "a" read the column 4 line 1, after "to", secondoccurrence, insert form lines 4 to 10, the right-hand portion of formula(III) should appear -as shown below instead of as in the patent:

Cl iame column 4, lines 22 to 3O the right-hand portion of the formulashould appear as shown below instead of as in the latent:

|C IC-NHCg-l olumn 5, line 59, for "power" read powder column 7, ines 52and 53, for "or", each occurrence, read for olumn 8, line 68, for "Cread C1 Signed and sealed this 16th day of October 1962.

SEAL) ttest:

RNEST W. SWIDER DAVID L. LADD ttesting Officer Commissioner of Patent 5

1. A COMPOUND OF THE FORMULA